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Publication numberUS4337028 A
Publication typeGrant
Application numberUS 06/153,057
Publication dateJun 29, 1982
Filing dateMay 27, 1980
Priority dateMay 27, 1980
Publication number06153057, 153057, US 4337028 A, US 4337028A, US-A-4337028, US4337028 A, US4337028A
InventorsMeredith J. Angwin, William C. Pfefferle
Original AssigneeThe United States Of America As Represented By The United States Environmental Protection Agency
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Catalytic monolith, method of its formulation and combustion process using the catalytic monolith
US 4337028 A
Abstract
A catalyst system in which the catalytic composition comprises a catalytically active material which is homogeneously interspersed throughout a monolith structure of ceramic composition. The composition is shaped into a unitary monolith which is employed as the catalyst structure. In the method the active material or materials are admixed with a ceramic material, which can be either active or inactive, in finely divided form and then shaped into the monolith structure.
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Claims(29)
What is claimed is:
1. A catalytically active structurally sound ceramic in a monolithic form having gas flow passages with heterogeneous combustion surfaces formed of a catalytically active mixed base metal oxide of the perovskite, spinel, corundum or ilmenite crystal structure for the sustained combustion of fuels.
2. A monolithic catalytic structure comprising a catalytically active mixed base metal oxide of the perovskite crystal structure ABO3 in intimate admixture with an additional base metal oxide of the perovskite crystal structure ABO3 suitable for forming structurally sound catalytic ceramics.
3. A catalytic structure as in claim 2 in which the active metal oxide is comprised of a metal of the cation B selected from the group consisting of Cr, Ni, Mn, Fe, Sr, and Ca.
4. A catalytic structure as in claim 2 in which the additional metal oxide is comprised of a metal of the cation A selected from the group consisting of La and Sr and is further comprised of a metal of the cation B selected from the group consisting of Al and Cr.
5. A monolithic catalytic structure comprising a catalytically active base metal oxide of the spinel crystal structure A[B2 ]O4 or B[AB]O4 in intimate admixture with an additional base metal oxide of the spinel crystal structure suitable for forming structurally sound catalytic ceramics.
6. A catalytic structure as in claim 5 in which the active metal oxide is comprised of a metal of the cation B selected from the group consisting of Ni, Fe and Cr.
7. A catalytic structure as in claim 5 in which the active metal oxide comprises Fe3 O4 or NiAl2 O4 and the additional metal oxide comprises MgAl2 O4.
8. A catalytic structure as in claim 5 in which the active metal oxide comprises Fe3 O4 with Cr.
9. A monolithic catalytic structure comprising a catalytically active base metal oxide of the corundum crystal structure B2 O3 or of the ilmenite crystal structure ABO3 in intimate admixture with an additional base metal oxide of the corundum crystal structure suitable for formation of a structurally sound catalytic ceramic.
10. A catalytic structure as in claim 9 in which the active metal oxide of the corundum structure is comprised of a metal of the cation B selected from the group consisting of Co and Fe.
11. A catalytic structure as in claim 9 in which the active metal oxide of the ilmenite structure is comprised of a metal selected from the group consisting of Fe and Cr.
12. A catalytic structure as in claim 10 or 11 in which the additional metal oxide is comprised of the metal Al of the cation B.
13. A catalytic structure as in claim 9 in which the active metal oxide comprises yttria-stabilized Co2 O3 of corundum crystal structure.
14. A combustion process comprising combusting reactants in the presence of a catalytically active structurally sound ceramic in a monolithic form having gas flow passages with heterogeneous combustion surfaces formed of a catalytically active base metal oxide of the perovskite, spinel, corundum or ilmenite crystal structure for the sustained combustion of fuels.
15. A combustion process comprising combusting reactants in the presence of a catalytically active structurally sound ceramic in a monolithic form having gas flow passages with heterogeneous combustion services formed of a catalytically active base metal oxide of the perovskite crystal structure ABO3 in intimate admixture with additional base metal oxide of the perovskite crystal structure ABO3 suitable for forming structurally sound catalytic ceramics.
16. A combustion process as in claim 15 in which the active metal oxide is comprised of a metal of the cation B selected from the group consisting of Cr, Ni, Mn, Fe, Sr, and Ca.
17. A combustion process as in claim 15 in which the additional metal oxide is comprised of a metal of the cation A selected from the group consisting of La and Sr and is further comprised of a metal of the cation B selected from the group consisting of Al and Cr.
18. A combustion process comprising combusting reactants in the presence of a monolithic catalytic structure comprising a catalytically active base metal oxide of the spinel crystal structure A[B2 ]O4 or B[AB]O4 in intimate admixture with an additional base metal oxide of the spinel crystal structure suitable for forming structurally sound catalytic ceramics.
19. A combustion process as in claim 18 in which the active metal oxide is comprised of a metal of the cation B selected from the group consisting of Ni, Fe and Cr.
20. A combustion process as in claim 18 in which the active metal oxide comprises Fe3 O4 or NiAl2 O4 and the additional metal oxide comprises MgAl2 O4.
21. A combustion process as in claim 18 in which the active metal oxide comprises Fe3 O4 with Cr.
22. A combustion process comprising combusting reactants in the presence of a monolithic catalytic structure comprising a catalytically active base metal oxide of the corundum crystal structure B2 O3 or of the ilmenite crystal structure ABO3 in intimate admixture with an additional base metal oxide of the corundum crystal structure suitable for formation of a structurally sound catalytic ceramic.
23. A combustion process as in claim 22 in which the active metal oxide of the corundum structure is comprised of a metal of the cation B selected from the group consisting of Co and Fe.
24. A combustion process as in claim 22 in which the active metal oxide of the ilmenite structure is comprised of a metal selected from the group consisting of Fe and Cr.
25. A combustion process as in claim 23 or 24 in which the additional metal oxide is comprised of the metal Al of the cation B.
26. A combustion process as in claim 22 in which the active metal oxide comprises yttria-stabilized Co2 O3.
27. A method of formulating a catalyst system comprising the steps of preparing an intimate admixture of a catalytically active base metal oxide having the perovskite crystal structure and an average particle size on the order of 10-20 microns with an additional base metal oxide having the perovskite crystal structure of the type suitable for formation of structurally sound catalytic ceramics and with an average particle size on the order of 10-20 microns, forming the mixture into a unitary structure, and calcining the formed structure.
28. A method of formulating a catalyst system comprising the steps of preparing an intimate admixture of a catalytically active base metal oxide of the spinel crystal structure and an average particle size on the order of 10-20 microns with an additional base metal oxide of the spinel crystal structure of the type suitable for formation of structurally sound catalytic ceramics and with an average particle size on the order of 10-20 microns, forming the mixture into a unitary structure, and calcining the formed structure.
29. A method of formulating a catalyst structure comprising the steps of preparing an intimate admixture of a catalytically active base metal oxide of the corundum crystal structure or of the ilmenite crystal structure, said active metal oxides having an average particle size on the order of 10-20 microns, with an additional base metal oxide of the corundum crystal structure of the type suitable for formation of structurally sound catalytic ceramics and having an average particle size on the order of 10-20 microns, forming the mixture into a unitary structure, and calcining the formed structure.
Description

The invention described herein was made in the course of, or under, a contract with the Environmental Protection Agency.

This invention relates to catalyst systems, compositions and methods for the formulation of such compositions. More particularly, the invention relates to catalyst systems in which the active material is homogeneously interspersed throughout a monolith structure of ceramic composition.

Presently known catalyst systems for use in applications such as combustors employ surface active materials in the form of pure pellets of the active material, or in the form of a surface coating of the active material on substrates such as ceramics. For example, it is well known to apply a catalyst material by slip coating onto a ceramic substrate which is in a honeycomb or other suitable monolith structure. For certain applications, such as gas turbine combustors, monolithic structures are most advantageous.

The disadvantages and limitations of conventional monolithic catalyst systems include the problem of loss of the active material by flaking off or volatilization from the substrate with a resulting loss in catalytic activity, or the problem of a change in the mechanical properties of the structures, due to an interaction of the catalyst coating and the monolith. In certain application, e.g. in combustors for gas turbines, the flaking material can cause erosion and damage to turbine blades, or the weakened catalyst/support can undergo thermostructural failure and enter the turbine, causing damage to the blades.

It is an object of the present invention to provide new and improved catalyst systems and compositions and methods of formulating the compositions.

Another object is to provide a catalyst system of the type described in which the active material is an integral part of the monolith structure to obviate the problems of coating flake-off or volatilization and consequent loss of catalytic activity.

Another object is to provide a catalyst system in which the integrity of the monolith structure is maintained during sustained combustion while obviating the problem of undesirable interaction of a catalyst metal with a substrate which results in structural weakening.

Another object is to provide a catalyst system which provides relatively longer operating life, especially in high temperature applications, and which provides good performance through relatively higher combustion efficiency over a long period of time.

Another object is to provide a catalyst system which achieves relatively good catalytic activity wherein the light-off temperatures of the systems compare favorably to the light-off temperatures of catalyst systems employing noble metals.

The invention in summary comprises a system in which the catalytic composition includes a catalytically active material which is homogeneously interspersed throughout a monolith structure of ceramic composition. The composition is shaped into a unitary monolith which is employed as the catalyst structure. In one version of the method the active material or materials are admixed with a ceramic material, which can be either active or inactive, in finely divided form and then shaped into the monolith structure which is calcined. The combustion process of the invention comprises combusting reactants in the presence of the monolithic catalytic structures.

The foregoing and additional objects and features of the invention will appear from the following specification in which the several embodiments are set forth.

The catalyst systems of the invention are comprised in general of a catalytically active metal oxide material homogeneously mixed or interspersed in a ceramic metal oxide material. The mixture can be shaped into a unitary monolith of the desired configuration. The resulting monolith is thereby comprised throughout of the catalytically active material to provide a catalysis system with a high degree of structural integrity and with improved performance.

In one embodiment of the invention the active material is a metal oxide which is homogeneously mixed throughout an inactive (or less active) metal oxide, which can be a mixed metal oxide.

Examples of the active metal oxides suitable for use in this embodiment include:

NiO

CeO2

Fe3 O4

CrO2

LaCrO3

Co2 O3

CoAl2 O4

Examples of the inactive (or less active) materials suitable for use in this embodiment include:

Zirconia Spinel

Yttria-stabilized zirconia

MgAl2 O4

SrZrO3

CaZrO3

Examples of the catalyst systems formed by the above materials for this embodiment include:

Zirconia Spinel doped with nickel oxide (5% by weight)

Yttria-stabilized zirconia doped with nickel oxide (5% by weight)

Cerium Oxide (80% by weight) with zirconia (20% by weight)

Cerium Oxide (17% by weight) with zirconia (78% by weight) with nickel oxide dopant (5% by weight)

SrCrO3 Perovskite doped with Co2 O3 (5% by weight)

CaZrO3 doped with Co2 O3 (5% by weight)

CaZrO3 arc-plasma sprayed with CoAl2 O4 doped with MgAl2 O4 (5% by weight)

SrZrO3 arc-plasma sprayed with CoAl2 O4 doped with MgAl2 O4 (5% by weight)

LaCrO3 (10% by weight) with ZrO2 (90% by weight)

Mg0.25 Ni0.75 Cr2 O4

MgAl2 O4 :Fe3 O4

In other embodiments of the invention the monolithic catalytic composition is of the perovskite, spinel, corundum or ilmenite crystal structure type in which primary catalytically active metal oxide materials are in intimate admixture with carriers comprising inactive or active metal oxide materials which are capable of forming ceramics. The resulting composition comprises a random interspersion of the various possible crystal structures, e.g. of the perovskites, or the spinels, or the corundum, or the ilmenite, as the case may be.

In one such embodiment a catalytically active base metal oxide of the perovskite crystal structure ABO3 forms a solid solution with another material (either active or inactive) comprising a metal oxide of the perovskite structure ABO3 suitable for formation of a ceramic. Generally the perovskite structure is comprised of cations of different types of metals, one of type A and another of Type B and in which the cations are of different size with the smaller cations in the ccp (cubic close packing) array occupying the octahedral holes formed exclusively by the oxide ions.

The following are examples of the primary active perovskite base metal oxides which can be employed in this embodiment:

LaCrO3

LaNiO3

LaMnO3

La0.5 Sr0.5 MnO3

La0.8 K0.2 Rh0.1 Mn0.9 O3

ZrXWO3 (X=Ni, Co)

LaCoFeO3

LaMNiO3 (M=Ca, or Sr)

The following are examples of perovskite type metal oxides suitable for use as carrier materials in this embodiment:

LaAlO3

(Sr0.4 La0.6)(Co0.5 V0.2)O3

(Sr0.2 La0.8)CoO3

(Sr0.4 La0.6)(Co0.9 Pt0.1)O3

The following are examples of catalytically active perovskite metal oxides in solid solution with perovskite metal oxides as carriers:

LaAlO3 :LaCrO3 (3:1 mole ratio)

LaAlO3 :LaNiO3 (3:1 mole ratio)

Another embodiment of the invention provides a primary catalytically active metal oxide of the spinel crystal structure in solid solution with a spinel structured compound which is suitable for formation of a ceramic. The spinel crystal structure takes the form A[B2 ]O4 or the inverse structure B[AB]O4.

The following are examples of the primary active spinel metal oxides which can be employed in this embodiment:

Fe3 O4 (Fe occupies both the A and B sites of the spinel A[B2 ]O4 crystal structure)

NiAl2 O4

Ni0.5 MgO0.5 (Al0.5 Cr0.3 Fe0.2)2 O4

Ni(Al0.3 Cr0.5 Fe0.2)2 O4 +NiO (1% by weight)

Co(Al0.3 Cr0.5 Fe0.2)2 O4 +CoO (5% by weight)

MgCr2 O4

The following is an example of a spinel type metal oxide suitable for use as the carrier material in this embodiment:

MgAl2 O4

The following are examples of the solid solutions of the catalytically active spinel materials with the carrier spinel materials:

MgAl2 O4 :NiAl2 O4 (3:1 mole ratio)

MgAl2 O4 :MgCr2 O4 (3:1 mole ratio)

MgAl2 O4 :Fe3 O4 (9:1 mole ratio)

Alternatively, an oxide cermet such as the following spinel cermet example can be used:

MgAl2 O4 :Fe3 O4 :(3:1 mole ratio)+40% Cr by weight

In another embodiment of the invention a primary catalytically active base metal oxide of either the corundum B2 O3 or ilmenite ABO3 crystal structures forms a solid solution with another material (either active or inactive) comprising a metal oxide of the corundum crystal structure suitable for formation of a ceramic.

Examples of the primary active corundum oxides include:

Fe2 O3

Co2 O3 stabilized with Yttria

Examples of the primary active ilmenite oxides employed in this embodiment include:

Cr2 O3 (Cr occupies both the A and B sites in the ilmenite ABO3 crystal structure)

Fex Mg1-x TiO3 (x between 0.85 and 0.90, for example)

An example of a corundum structured compound suitable for use in this embodiment as the ceramic carrier comprises alumina.

Examples of solid solutions formed between ilmenite structured active compounds and the corundum structured carrier comprise Cr2 O3 :Al2 O3 (1:5 mole ratio) and Fe0.85 Mg0.15 TiO3 :Al2 O3 (1:9 mole ratio) respectively.

Examples of solid solutions between active compounds and carriers which are both of corundum structure include:

Al2 O3 :Fe2 O3 (3:1 mole ratio)

Al2 O3 :Co2 O3 (5:1 mole ratio) stabilized with Yttria (2% by weight)

From the potentially large number of metal oxide compounds which could formulate into solid solutions of the foregoing type, it will be realized that those compounds containing metals with volatile oxides are generally unsuitable for combustor service. Thus, the many compounds containing barium, lead, rhenium, ruthenium, sodium and other volatile metals are not preferred. Similarly, compounds containing halogens are not considered useful for combustor service and are not preferred in this invention. Additionally, compounds of the type with known melting points below about 1873 K are suitable only for lower temperature applications.

One method of formulating the catalyst systems of the invention comprises selection of the starting material in a predetermined proportion according to the mole weight formula of the composition desired for the resulting monolith structure. The starting compounds are pulverized and intermixed, such as by a ball mill or other method, to insure complete dispersion and a small particle size on the order of 10 to 20 microns. The mixture of powder is then formed into the shape which is desired for the particular ceramic technique which is to be used to form the catalyst structure. The mixture is then fired at a temperature of at least 1000 C.

As one example of a method of molding the catalyst structure to a desired shape, e.g. a honeycomb shape, would be to form an aqueous or organic slurry with the reactive powders and a binder, pour the slurry into a mold, apply heat to drive off the water and binder, and then sinter at the high temperature. Another example would be to apply a coating of such a mixture to a substrate such as paper formed into the desired shape and then burn the paper off. Another example for use where one of the starting materials is a pure compound such as alumina would be to press the powders together into the desired shape and then cause them to react.

The following is a specific example of a method of formulating a perovskite-based catalyst system which is a solid solution of LaAlO3 and LaCrO3. Ammonium dichromate (NH4)2 Cr2 O3 is dissolved in deionized water. Added to that solution is the appropriate mole percentage of La2 O3. Added to that mixture is a reactive alumina in the appropriate mole percentage. The resulting mixture is dried at about 150 C. to form a sludge, then calcined at a temperature above about 600 C. The resulting powder is ball milled and then recalcined above 1300 C. A sample of the recalcined material may be checked by X-ray diffraction. If reaction is not complete, the powder is recalcined until the desired state is achieved.

At this stage the powder which has been made is a completely reacted composition of the base metal oxide. The reacted powder is ball milled with water or other suitable liquid to develope a rheology suited to the chosen forming method, then formed and shaped into the desired unitary configuration.

Another method for making materials suitable for this invention is by gelling solutions of the proper composition of the desired metals. In this case the gel may be spray-dried to provide a powder of the proper rheology for further processing.

After the powder has been brought to the proper rheology, the shaping step may be carried out by formation of a water-based slip (with appropriate organic binders and dispersants) and then casting, extruding, molding or pressing the material into the desired shape. This step may comprise coating of the slip onto a paper, polymer or sponge substrate, after which the substrate can be removed as by firing.

The final step in this method is calcining the resultant monolith material in the range of 1100-1600 C. It is preferable to calcine in an oxidizing atmosphere. However, with constituents having oxides such as Cr2 O3, which have some volatility, it may be necessary to calcine under an inert atmosphere such as argon. If the material is calcined under a forming gas to reduce the chance of oxide vaporization, a sample of it must be checked by X-ray diffraction to make sure that segregated reduced phases have not been introduced.

The following is a specific example of a method of forming a catalyst system with a corundum-based active ceramic. In the first step appropriate mole percentages of (NH4)2 Cr2 O7 and Al2 O3 (reactive) are added to deionized water using suitable dispersants. The slurry is dried at 150 C. to a sludge, the sludge is calcined at a temperature of 600 C. and the resulting powder is ball milled. The remaining steps are carried out as set forth in the above example for the perovskite-based system.

The following is a specific example of a method of forming a spinel-based metal oxide catalyst system which is a solid solution of MgAl2 O4 and NiAl2 O4. Basic magnesium carbonate MgCO3.Mg(OH)2. 3H2 O is dispersed in deionized water, and to that mixture are added suitable quantities of reactive Al2 O3 and Ni(CO3). The product is then dried at 150 C. to a sludge, and the sludge is calcined at a temperature range of 1000 C.-1300 C. The remaining steps are carried out as in the above-described example for the method of preparing the perovskite-based system.

The following is a specific example of a method of formulating another spinel-based system which is a solid solution of MgAl2 O4 and MgCr2 O4. In the first step (NH4)2 Cr2 O7 is dispersed in deionized water. To that mixture appropriate quantities of basic magnesium carbonate and reactive Al2 O3 are added as well as a dispersant. The remaining steps are carried out as described in the immediately preceding example.

In the method of forming catalyst systems based upon the above-described general ceramic materials, a common catalytic substrate having several percent (preferably from 1 to 10% but up to 25%) of a catalytically active metal oxide is added to the material before monolith formation. For example, nickel oxide in yttria-stabilized zirconia; nickel oxide or chromium oxide in mullite or cordierite or zircon mullite; LaCrO3 and mullite; MgCr2 O4 and alumina; or nickel oxide or Co2 O3 and alumina. The material is then shaped as described above in connection with the perovskite-based system. Longer times at calcining temperatures may be required to insure that any solid state reaction is complete during formulation.

Another preferred embodiment of the present invention is the use of catalytically-active oxide composition as both the catalytic and the structural materials. Although there are many advantages to be gained by mixing active materials with less-active materials, it is often desirable to use the active oxide composition for the catalytic and structural materials. An example of this is the use of LaCrO3 as the performing catalytically active, electrically-conducting monolith material.

EXAMPLE I

Oxide powders of MgAl2 O4 and NiAl2 O4 (3:1 mole ratio) were prepared by pressing the powders into discs and calcining in the manner described above. The disc size was 21/4" in diameter and 11/4" long with 18 to 30 holes of 0.25" diameter drilled axially to form gas flow passages. The resulting monolith structure was tested in a combustor using air and natural gas reactants under fuel-lean conditions down to a minimum preheat of 325 F. Blowout of the catalyst bed did not occur at the highest throughput attained, 849,000 hr-1 space velocity. The catalyst was also tested on lean diesel fuel and sustained combustion to a minimum preheat of 590 F. During the diesel fuel test blowout did not occur during maximum throughput at a space velocity of 1,152,000 hr-1.

The results of the test of the first example are listed in Table I. CO emissions were below 50 ppm, and NO emissions ranged from 1 to 30 ppm.

EXAMPLE II

Powders of LaAlO3 and LaCrO3 (3:1 mole ratio) were pressed and calcined into discs shaped as described for Example I. The catalyst was tested in a combustor using reactants of air and natural gas as well as diesel fuel. The test results are depicted in Table II.

EXAMPLE III

Powders of MgAl2 O4 and Fe3 O4 (3:1 mole ratio) were pressed and calcined into pellets shaped as described in Example I. The catalyst was tested in a combustor on lean natural gas and lean diesel fuel. The test results are set forth in Table III.

EXAMPLE IV

Powders of MgAl2 O4 and MgCr2 O4 (3:1 mole ratio) were pressed and calcined into the shape of tubes 2" in length having nominal dimensions of 1/4" OD and 1/8" ID. Forty-four of these tubes were bundled and wrapped together in insulation and supported vertically within a holder tube on a disc of Torvex alumina 1" long by 2" diameter which was honeycombed with 3/16" diameter cells. The catalyst structure was tested on air and lean and rich natural gas and diesel fuel. The results of the test are depicted in Table IV. The performance shows that on lean natural gas CO and NO emissions were at or below 18 and 10 ppm respectively. There was no loss in catalytic activity after 5 hours of testing.

EXAMPLE V

Powders of Al2 O3 and Cr2 O3 (9:1 mole ratio) were pressed and calcined into the shape of tubes 2" in length having nominal dimensions of 1/4" OD and 1/8" ID. A plurality of the tubes were bundled, wrapped together and supported in the manner described above for example IV. Platinum was added to the front segment to promote light-off. The catalyst structure was tested on air and natural gas. The results of the test are depicted in Table V.

From the foregoing it will be seen that the catalyst system compositions of the present invention provide good performance with high combustion efficiency over a long period of time. The catalytic monolith maintains its structural integrity in operation without loss of catalytic activity through flake-off or volatilization. There is no problem of interaction of base metal catalysts with the substrate, nor is there the problem of degradation of surface area due to growth in crystallite size of the active component when in operation so that there is a relatively longer life, especially in high temperature applications. Additionally, the manufacturing process is relatively less expensive in that there are fewer steps to formulate the monolith structure as compared to existing techniques of manufacturing a substrate, applying a wash coat and then applying the catalyst.

While the foregoing embodiments are at present considered to be preferred, it is understood that numerous variations and modifications may be made therein by those skilled in the art and it is intended to cover in the appended claims all such variations and modifications as fall within the true spirit and scope of the invention.

                                  TABLE I__________________________________________________________________________Test    TA SV   .mfuel            .mair                  Tph                     Tbed                       Velocity                            CO  NO  UHC Qpoint    (%)  (l/hr)       (lbm/hr)            (lbm/hr)                 (F.)                    (F.)                       (ft/sec)                            (ppm)                                (ppm)                                    (ppm)                                        (Btu/hr)                                             Test type__________________________________________________________________________41-6    191  387,000       2.36 77.4 668                    2000                       9.0  10  4   0   50,700                                             Stabilizing41-7    "  "    "    "    618                    2025                       "    "   "   "   "    on natural41-8    "  "    "    "    613                    2020                       "    "   "   "   "    gas41-9    "  "    "    "    610                    2020                       "    "   "   "   "    "41-10    "  "    "    "    610                    2020                       "    13  "   1   "    "41-11    "  "    "    "    609                    2010                       "    10  "   0   "    "41-12    "  "    "    "    610                    "  "    "   "   "   "    "41-13    "  "    "    "    608                    "  "    "   "   "   "    "41-14    "  "    "    "    607                    "  "    "   5   "   "    "41-15    "  "    "    "    607                    2005                       "    8   "   "   "    "41-16    "  "    "    "    609                    2005                       "    "   "   "   "    "41-17    188  381,000       2.36 77.4 575                    2010                       8.6  6   5   0   50,700                                             Minimum pre-41-18    186  376,000       "    75.2 550                    2010                       8.7  8   "   "   "    heat, lean,41-19    183  372,000       "    74.2 500                    2010                       8.6  8   "   "   "    on natural41-20    181  367,000       "    73.3 475                    2005                       8.5  10  "   "   "    gas41- 21    174  353,000       "    70.4 450                    "  8.2  "   6   "   "    "41-22    172  349,000       "    69.4 425                    "  8.1  "   "   "   "    "41-23    169  344,000       "    68.4 400                    "  8.0  9   "   "   "    "41-24    162  330,000       "    65.5 375                    2015                       7.7  10  7   "   "    "41-25    160  326,000       "    64.5 350                    2005                       7.5  "   8   "   "    "41-26    157  321,000       "    63.6 325                    2005                       7.4  "   8   "   "    "41-27    152  312,000       "    61.6 335                    2015                       7.2  "   9   "   "    "41-3452  219,000       4.29 38.4 523                    1960                       5.1  --  2   6800                                        92,200                                             Rich conditions41-3752  219,000       4.29 38.4 658                    2030                       5.1  --  1   3100                                        92,200                                             on natural gas,                                             unstable41-40    198  399,000       2.36 80.0 801                    2015                       9.2  --  5   0   50,700                                             Maximum41-41    204  495,000       2.84 99.4 793                    2060                       11.5 --  4   "   61,100                                             throughput,41-42    193  545,000       3.30 109. 790                    2070                       12.6 43  5   "   71,000                                             natural gas,41-43    212  687,000       3.81 138. 793                    2085                       15.9 43  3   "   82,000                                             lean41-44    249  849,000       4.02 172. 789                    2025                       19.7 40  2   "   86,400                                             "41-47    173  365,000       2.89 77.1 708                    2090                       8.5  0   16  0   62,100                                             Minimum pre-41-48    "  "    "    "    692                    2115                       "    45  "   "   "    heat, lean,41-49    "  "    "    "    663                    2115                       "    43  "   "   "    condensed fuel41-50    "  "    "    "    642                    2110                       "    38  "   "   "    "41-51    "  "    "    "    626                    2100                       "    45  15  "   "    "41-52    170  356,000       "    75.2 603                    2075                       8.2  48  16  "   "    "41-53    170  356,000       "    75.2 596                    2025                       8.2  25  17  "   "    "41-58    164  356,000       2.97 75.2 876                    2140                       8.2  44  30  0.5 54,100                                             Maximum41-59    171  425,000       3.41 89.7 863                    2200                       9.8  --  --  --  62,200                                             throughput41-60    181  562,000       4.26 119. 860                    2100                       13.0 40  25  0.5 77,700                                             diesel fuel,41-61    188  677,000       4.92 143. 872                    2260                       15.7 40  23  "   89,700                                             lean41-62    178  723,000       5.58 153. 878                    2325                       16.7 --  33  "   101,700                                             "41-63    194  883,000       6.23 186. 895                    2350                       20.5 13  24  "   113,600                                             "41-64    200  1,152,000       7.87 243. 867                    2240                       26.7 15  18  "   143,500                                             "41-65    185  1,152,000       8.53 243. 860                    2340                       26.7 30  21  "   155,500                                             "__________________________________________________________________________

                                  TABLE II__________________________________________________________________________Test    TA SV   .mfuel            .mair                  Tph                     Tbed                       Velocity                            NO  UHC Qpoint    (%)  (l/hr)       (lbm/hr)            (lbm/hr)                 (F.)                    (F.)                       (ft/sec)                            (ppm)                                (ppm)                                    (Btu/hr)                                         Test type__________________________________________________________________________42-4    191  460,000       2.36 77.4 630                    2120                       10.6 3   0   50,700                                         Stabilizing on42-5    "  "    "    "    630                    2110                       "    4   1   "    natural gas42-6    "  "    "    "    630                    "  "    4   "   "    "42-7    "  "    "    "    631                    "  "    4   "   "    "42-8    "  "    "    "    631                    "  "    5   "   "    "42-9    "  "    "    "    632                    "  "    5   "   "    "42-10    "  "    "    "    634                    2120                       "    6   "   "    "42-11    191  460,000       2.36 77.4 570                    2110                       10.6 6   1   50,700                                         Minimum preheat42-12    183  442,000       "    75.2 548                    2110                       10.2 "   "   "    lean, natural42-13    181  437,000       "    73.3 525                    2100                       10.1 "   "   "    gas42-14    174  421,000       "    70.4 500                    2100                       9.7  "   "   "    "42-15    169  410,000       "    68.4 450                    2090                       9.4  7   "   "    "42-16    162  393,000       "    65.5 425                    2100                       9.1  8   "   "    "42-17    157  382,000       "    63.6 400                    2110                       8.9  9   "   "    "42-18    157  382,000       "    63.6 377                    2100                       8.9  8   "   "    "42-1952  260,000       4.29 38.4 500                    2120                       6.0  4   5300                                    92,200                                         Minimum preheat,42-2056  277,000       "    41.3 474                    2110                       6.4  3   2500                                    "    rich, natural42-2156  277,000       "    41.3 450                    2100                       6.4  3   3000                                    "    gas42-2260  293,000       "    44.2 390                    1970                       6.8  6    900                                    "    "42-2363  284,000       "    46.2 375                    2025                       7.0  16   400                                    "    "42-25    206  589,000       1.05 99.4 690                    2125                       13.6 7   1   60,600                                         Maximum42-26    210  703,000       1.23 119. 689                    2100                       16.3 7   "   71,000                                         throughput,42-27    207  789,000       1.40 133. 689                    2160                       18.3 7   "   80,600                                         natural gas,42-28    214  874,000       1.50 148. 691                    2160                       20.2 6   "   86,400                                         lean42-29    184  425,000       2.66 75.5 790                    2140                       9.8  --  --  48,500                                         Minimum preheat,42-30    "  "    "    "    766                    2140                       "    11  4   "    lean, diesel fuel42-31    "  "    "    "    725                    2160                       "    12  3   "    "42-32    "  "    "    "    700                    2160                       "    13  "   "    "42-33    182  420,000       "    74.5 650                    2140                       9.7  12  "   "    "42-34    172  398,000       "    70.6 623                    2150                       9.2  15  "   "    "42-35    161  371,000       "    65.8 600                    1770                       8.6  20  2   "    "42-37    196  753,000       4.43 133.5                 750                    2240                       17.4 12  18  80,800                                         Maximum through-42-38    189  944,000       5.74 167. 772                    2140                       21.8 18  17  10,500                                         put, diesel fuel,42-39    191  1,124,000       6.76 199. 792                    1650                       26.0 16  15  123,000                                         lean__________________________________________________________________________

                                  TABLE III__________________________________________________________________________Test    TA SV    .mfuel            .mair                 Tph                    Tbed                       Velocity                            CO  NO  UHC Qpoint    (%)  (l/hr)       (lbm/hr)            (lbm/hr)                 (F.)                    (F.)                       (ft/sec)                            (ppm)                                (ppm)                                    (ppm)                                        (Btu/hr)                                             Test Type__________________________________________________________________________45-2    191  395,000       2.36 77.4 730                    2260                       11.4 --  4   0   50,700                                             Stabilizing on45-3    "  "    "    "    "  "  "    --  5   3   "    natural gas45-4    "  "    "    "    "  "  "    --  5   0   "    "45-5    "  "    "    "    "  "  "    --  5   "   "    "45-6    "  "    "    "    "  "  "    --  4   "   "    "45-7    "  "    "    "    "  "  "    --  5   "   "    "45-11    191  395,000       2.36 77.4 778                    2280                       11.4 25  6   0   50,700                                             Minimum pre-45-12    "  "    "    "    774                    2280                       "    20  5   "   "    heat, lean,45-13    "  "    "    "    700                    2250                       "    20  4   "   "    natural gas45-14    "  "    "    "    675                    2240                       "    25   4  "   "    "45-15    179  371,000       "    72.6 625                    2250                       10.8  0  6   2   "    "45-16    179  371,000       "    72.6 600                    "  10.8 "   5   "   "    "45-17    175  362,000       "    70.6 575                    "  10.5 "   6   "   "    "45-18    172  357,000       "    69.7 550                    "  10.3 "   "   "   "    "45-19    170  353,000       "    68.7 525                    2240                       10.2 "   "   "   "    "45-20    167  348,000       "    67.7 500                    2240                       10.1 "   "   "   "    "45-26    191  395,000       2.36 77.4 860                    2200                       11.4  0  7   0   50,700                                             Maximum45-27    211  604,000       3.30 119. 824                    2240                       17.5 "   5   "   71,000                                             throughput,45-28    214  702,000       3.78 138. 817                    2250                       20.3 "   4   "   81,300                                             natural gas45-29    213  751,000       4.05 148  806                    2250                       21.8 "   4   "   87,100                                             "45-30    187  388,000       2.79 80.3 794                    2310                       11.2 --  15  0   50,900                                             Minimum pre-45-31    182  379,000       "    78.4 750                    2300                       11.0 --  14  "   "    heat, lean,45-32    182  379,000       "    78.4 700                    2320                       11.0 --  15  "   "    diesel45-33    182  379,000       "    78.4 650                    2300                       11.0 --  "   "   "    "45-34    180  374,000       "    77.4 625                    "  10.8 --  "   "   "    "45-35    176  365,000       "    75.5 600                    "  10.6 --  "   "   "    "45-36    171  355,000       "    73.5 575                    "  10.3 --  17  "   "    "45-37    167  346,000       "    71.6 550                    "  10.0 --  17  "   "    "45-38    162  337,000       "    69.7 525                    "  9.8  --  18  "   "    "45-39    158  327,000       "    67.7 490                    2320                       9.5  --  21  "   "    "45-40    153  318,000       "    65.8 475                    2350                       9.2  --  23  "   "    "45-41    153  318,000       "    65.8 450                    2300                       9.2  --  22  "   "    "45-42    149  309,000       "    63.9 425                    2340                       8.9  --  23  "   "    "45-43    144  299,000       "    61.9 395                    2340                       8.7  --  28  "   "    "45-44    142  295,000       "    61.0 375                    2340                       8.5  --  28  "   "    "45-45    142  295,000       "    61.0 348                    2340                       8.5  --  28  "   "    "45-46    140  290,000       "    60.0 325                    2300                       8.4  --  26  "   "    "45-47    137  285,000       "    59.0 300                    2270                       8.3  --  23  "   "    "45-48    122  253,000       "    52.3 275                    2250                       7.3  --  26  "   "    "45-49    117  243,000       "    50.3 255                    2150                       7.0  --  20  "   "    "45-52    182  374,000       2.89 77.4 794                    2280                       10.8 --  11  2   527,000                                             Maximum45-53    203  669,000       4.42 138. 781                    2350                       19.4 --  8   3   806,000                                             throughput,45-54    194  814,000       5.64 168. 794                    2300                       23.6 --  15  2   103,000                                             diesel fuel45-55    174  879,000       6.79 182. 793                    2000                       25.5 --  30  --  124,000                                             "45-56    140  290,000       2.79 60.0 351                    2170                       8.4  --  28  3   50,900                                             Minimum pre-45-57    119  435,000       4.92 90.0 321                    2250                       12.6 --  --  --  89,700                                             heat, lean,45-58    119  435,000       4.92 90.0 304                    2220                       12.6 --  --  --  89,700                                             diesel at                                             higher through-                                             put__________________________________________________________________________

                                  TABLE IV__________________________________________________________________________Test    TA SV    .mfuel             . mair                   Tph                      Tbed                         Velocity                               CO  NO  HC  Qpoint    (%)  (l/hr)        (lbm/hr)             (lbm/hr)                   (F.)                      (F.)                         (ft/sec)                               (ppm)                                   (ppm)                                       (ppm)                                           (Btu/hr)                                                Test__________________________________________________________________________                                                type46-2    222  321,000        2.36 90.0  724                      2450                         14.9   8  4   0   50,700                                                Minimum preheat46-3    222  321,000        "    90.0  699                      2450                         14.9  10  5   "   "    lean, natural46-4    218  315,000        "    88.1  640                      2450                         14.6  10  7   "   "    gas46-5    203  295,000        "    82.3  611                      2400                         13.7  13  "   "   "    "46-6    199  288,000        "    80.3  575                      2425                         13.4  13  "   "   "    "46-7    196  285,000        "    79.4  550                      2350                         13.2  15  "   "   "    "46-8    191  279,000        "    77.4  525                      -- 12.9  --  --  "   "    "46-9    187  272,000        "    75.5  500                      2480                         12.6  15  8   "   "    "46-10    182  265,000        "    73.5  475                      2550                         12.3  "   "   "   "    "46-11    "  "     "    "     450                      2620                         "     "   "   "   "    "46-12    "  "     "    "     425                      2600                         "     "   "   "   "    "46-13    "  "     "    "     400                      2550                         "     13  "   "   "    "46-14    179  262,000        "    72.6  375                      2500                         12.1  --  "   "   "    "46-15    179  262,000        "    72.6  350                      2550                         12.1  15  "   "   "    "46-16    179  262,000        "    72.6  325                      2525                         12.1  10  "   "   "    "46-17    175  255,000        "    70.6  300                      2525                         11.8  15  "   "   "    "46-18    175  255,000        "    70.6  275                      2500                         11.8  "   "   "   "    "46-19    175  255,000        "    70.6  250                      2500                         11.8  "   "   "   "    "46-20    170  249,000        "    68.7  178*                      2450                         11.5  "   "   "   "    "46-2350  152,000        4.29 36.8  674                      2620                          7.0  --  6   6000                                           92,000                                                Unstable on nat-                                                ural gas, rich46-25    234  338,000        2.36 94.8  824                      2450                         15.7  18  10  0   50,700                                                Maximum through-46-26    227  390,000        2.82 109.  780                      2450                         18.1  15  8   "   60,600                                                put, lean, nat-46-27    212  426,000        3.27 119.  780                      2480                         19.7  13  "   "   70,300                                                ural gas46-28    208  479,000        3.75 134.  789                      2525                         22.2  15  "   "   80,600                                                "46-29    213  530,000        4.05 148.  788                      2500                         24.5  10  "   "   87,100                                                "46-32    207  307,000        2.82 90.0  780                      2550                         14.2  20  7   0   60,600                                                Unstable on46-33    207  307,000        2.82 90.0  804                      2500                         14.2  10  8   1   60,600                                                diesel fuel46-35    175  472,000        5.12 138.  850                      -- 21.9  10  9   10  112,600                                                "46-37    191  279,000        2.36 77.4  525                      2450                         12.9   5  5   0   50,700                                                Still catalyti-46-38    191  279,000        2.36 77.4  497                      2450                         12.9   5  5   --  50,700                                                cally active on                                                natural__________________________________________________________________________                                                gas *Ambient

                                  TABLE V__________________________________________________________________________Test    TA SV    .mCH.sbsb. 4             .mm air                  Tph                     Tbed (F.)                           CO  NO  HCPoint    (%)  (l/hr)        (lbm/hr)             (lbm/hr)                  (F.)                     TR1                        TR2                           (ppm)                               (ppm)                                   (ppm)                                       Test Type__________________________________________________________________________32-10    180  116,000        2.44 75.7 683                     2520                         800                           20  30  8   Aging (bed nonuniform)32-12    197  116,000        2.23 "    685                     2600                        1560                           16  28  12  "32-14    207  115,000        2.12 "    688                     2575                        1775                           18  22  9   "32-15    "  "     "    "    689                     2575                        1840                           20  23  --  "32-16    "  "     "    "    688                     2560                        1850                           20  21  --  "32-17    "  "     "    "    689                     2575                        1910                           25  21  --  "32-18    213  "     2.06 "    690                     2600                        2125                           19  22  --  "32-20    205  111,000        "    72.7 689                     2590                        2100                           16  20  --  "32-21    "  "     "    "    690                     2570                        1900                           16  19  --  "32-23    "  "     "    "    "  2560                        1810                           20  15  --  "32-24    "  "     "    "    "  "  1890                           21  15  --  "32-25    "  "     "    "    "  "  1950                           19  20  1   "32-26    "  "     "    "    691                     2580                        2100                           21  20  1   "32-27    "  "     "    "    "  "  2100                           22  18  2   "32-28    "  "     "    "    "  "  2110                           23  18  2   "32-29    "  "     "    "    "  2575                        1200                           21  16  2   "32-30    "  "     "    "    "  2575                        1690                           20  16  2   "32-31    "  "     "    "    690                     2580                        1750                           20  14  2   "32-32    "  "     "    "    690                     "  1740                           20  14  1   "32-33    "  "     "    "    691                     "  1710                           21  14  1   "32-34    "  "     "    "    "  "  1740                           20  14  1   "32-35    "  "     "    "    "  "  1810                           21  14  0   "32-36    "  "     "    "    690                     2525                        1640                           20  13  0   "32-41    245  123,000        1.93 81.5 778                     2575                        2560                            4   3  1   Minimum preheat, lean32-42    242  123,000        1.96 "    761                     2560                        2550                            5   3  0   "32-43    235  124,000        2.01 "    745                     2580                        2560                            5   3  0   "32-45    235  "     2.01 "    725                     2550                        2525                            5   3  0   "32-47    218  "     2.17 "    698                     2575                        2550                            5   4  0   "32-48    205  "     2.31 "    675                     2600                        2580                            5   5  3   "32-49    205  "     2.31 "    646                     2580                        2560                            5   4  2   "32-50    201  125,000        2.36 "    623                     2590                        2570                            5   5  2   "32-51    196  125,000        2.41 "    599                     2575                        2550                            5   4  3   "32-52    193  123,000        2.41 80.1 574                     2570                        2550                            5   4  2   "32-54    190  126,000        2.52 82.5 582                     2600                        2590                            5   5  1   "32-56    188  143,000        2.87 93.2 550                     2600                        2590                            5   5  2   "32-57    160  126,000        2.95 81.5 500                     2575                        2550                            6   4  0   "32-58    176  137,000        "    89.3 440                     2560                        "   6   4  0   "32-59    176  137,000        "    89.3 400                     2570                        "   6   4  0   "32-61    179  121,000        2.55 78.6  750*                     2500                        2490                            6   4  0   "32-62    173  107,000        2.33 69.4  762*                     2500                        2490                            6   4  0   "32-65    210  154,000        2.79 101  645                     2600                        2575                            5   4  0   Maximum throughput32-66    217  219,000        3.82 144  649                     "  --  6   4  0   "32-67    216  229,000        4.05 150  656                     "  --  6   4  0   "32-68    218  232,000        4.05 152  646                     "  2560                            6   4  0   "__________________________________________________________________________
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Classifications
U.S. Classification431/7, 502/307, 423/213.2, 502/316, 502/301, 502/324, 502/330, 502/314, 502/302, 502/332, 502/306, 423/213.5
International ClassificationB01J23/76, B01J21/00, B01J23/74, F23C13/00, B01J35/04
Cooperative ClassificationB01J35/04, B01J21/005, F23C13/00, B01J23/74, B01J23/76
European ClassificationF23C13/00, B01J23/76, B01J21/00S, B01J35/04, B01J23/74
Legal Events
DateCodeEventDescription
Jun 15, 1981ASAssignment
Owner name: UNITED STATES OF AMERICA AS REPRESENTED BY THE ADM
Free format text: ASSIGNS THE ENTIRE INTEREST, SUBJECT TO LICENSE RECITED.;ASSIGNOR:ACUREX CORPORATION;REEL/FRAME:003863/0011
Effective date: 19810529